Thermosettable prepolymer prepared from heterocyclic material having alkyl substituents, mono- or dianhydride, ethylenically unsaturated material and a hydroxide, carbonate of bicarbonate of a metal of groups I-A or II-A

Abstract

Thermosettable prepolymers are prepared by reacting (A) the reaction product of (1) a heterocyclic material having one or more rings therein, at least one nitrogen atom in a ring and at least two substituent groups which have at least one reactive hydrogen atom attached to a carbon atom which is attached to a heterocyclic ring such as 2,3,5,6-tetramethylpyrazine; (2) a cycloaliphatic or aromatic carboxylic acid mono- or dianhydride such as pyromellitic dianhydride; and (3) a compound containing both a polymerizable ethylenically unsaturated group and at least one group selected from (a) a heterocyclic material having one or more rings, at least one nitrogen atom in a ring and at least one substituent group which has at least one reactive hydrogen atom attached to a carbon atom which is attached to a heterocyclic ring such as 2-methyl-5-vinyl pyridine or (b) a cycloaliphatic or aromatic carboxylic acid mono- or dianhydride group such as cis-5-norbornene-endo-2,3-dicarboxylic anhydride; with (B) an aqueous or alcoholic solution of a hydroxide, carbonate or bicarbonate of a metal of Groups I-A or II-A, such as sodium hydroxide. These prepolymers when subjected to a thermoset condition by heat and pressure or by homopolymerization in the presence of or copolymerization with an N,N'-bis-imide exhibit good char forming properties when subjected to a temperature of 700° C.

I claim: 
     
       1. A cured product resulting from curing in the presence of or copolymerization with a N,N'-bis-imide, a thermosettable prepolymer prepared by reacting (A) the reaction product of (1) a heterocyclic material having one or more rings therein, at least one nitrogen atom in a ring and at least two substituent groups which have at least one reactive hydrogen atom attached to a carbon atom which is attached to a heterocyclic ring;   (2) a cycloaliphatic or aromatic carboxylic acid mono- or dianhydride; and   (3) a compound containing both a polymerizable ethylenically unsaturated group and at least one group selected from (a) a heterocyclic material having one or more rings, at least one nitrogen atom in a ring and at least one substituent group which has at least one reactive hydrogen atom attached to a carbon atom which is attached to a heterocyclic ring or   (b) a cycloaliphatic or aromatic carboxylic acid mono- or dianhydride group; with       (B) an aqueous or alcoholic solution of a hydroxide, carbonate or bicarbonate of a metal of groups I-A or II-A; and wherein the components of (A) are employed in a molar ratio of (1):(2):(3) of from about 1:0.25:0.25 to about 1:4:4, respectively and components A and B are present in quantities which are sufficient to react at least a portion of any anhydride, lactone, or combination of both anhydride and lactone groups present in component (A) with component (B).     
     
     
       2. A product of claim 1 wherein (a) component (A-1) is a pyrazine or pyridine;   (b) component (A-2) is represented by the formula ##STR16##  wherein R is a cycloaliphatic or aromatic group; (c) component (A-3) is a (1) pyridine or (2) cyclic carboxylic acid monoanhydride represented by the formula ##STR17##   in which R is a hydrogen, halogen or a 1 to 4 carbon alkyl group and X is either --CH 2  --, --CH 2  CH 2  --, --O--, --NH--, --CCl 2  -- or --S--; and   (d) component (B) is an alkali metal hydroxide;   (e) the components of (A) are employed in a molar ratio of (1):(2):(3) of from about 1:0.5:0.5 to about 1:1.5:1.5, respectively; and   (f) components A and B are present in quantities which are sufficient to react from about 10 to about 100 percent of the anhydride and lactone groups remaining in component (A) with component (B).   
     
     
       3. A product of claim 2 wherein components (A) and (B) are present in quantities which are sufficient to react from about 50 to about 100 percent of the anhydride and lactone groups present in component (A) with component (B). 
     
     
       4. A product of claim 3 wherein (a) component (A-1) is 2,3,5,6-tetramethylpyrazine, 2,4,6-trimethylpyridine, or combination thereof;   (b) component (A-2) is pyromellitic dianhydride, phthalic anhydride, or combination thereof; and   (c) component (A-3) is 2-methyl-5-vinylpyridine, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, or combination thereof.   
     
     
       5. A cured product of claim 1, 2, 3 or 4 wherein said N,N'-bis-imide is 1,1'-(methylenedi-4,1-phenylene)-bismaleimide. 
     
     
       6. A cured product of claim 1, 2, 3 or 4 which contains a reinforcing material. 
     
     
       7. A cured product of claim 5 which contains a reinforcing material.